Near infrared absorbing phthalocyanines and their use

ABSTRACT

The instant invention relates to novel phthalocyanines and their use as IR-absorbers, in particular in transparent thermoplastic or crosslinkable polymers. A further aspect of the invention is a composition of these phthalocyanines and thermoplastic or crosslinkable polymers and an architectural or automotive glazing containing these phthalocyanines.

The instant invention relates to novel phthalocyanines and their use asIR-absorbers, in particular in transparent thermoplastic orcrosslinkable polymers. A further aspect of the invention is acomposition of these phthalocyanines and thermoplastic or crosslinkablepolymers and an architectural or automotive glazing containing thesephthalocyanines.

The absorption of near infrared radiation (NIR) is an importanttechnical issue in various fields. A significant reduction of the heattransfer into buildings and cars is possible by blocking or filteringthe near infrared part of the solar spectrum. This allows a considerableenergy saving, mainly due to a smaller demand for air conditioning.

Up to now several solutions have been proposed and more and more havebeen applied on glazing surfaces of many buildings, such as interferencereflective films, semi-conducting or conducting films: they are all ableto reflect, with good selectivity, NIR radiation. The so-called “low-e”windows are for example reflective coated mineral or polymeric glasses.However the production of such coatings is an extremely time consumingstep, specially considering that almost all solutions need severallayers, and that the durability may be also quite limited due to agenerally low scratch resistance. This is, for example, described in WO2005/072947.

Another approach is the use of bulk additives that absorb the NIRradiation. This approach is less expensive, not time consuming, longlasting and particularly needed for thermoplastic polymers used inglazing. Some examples for polymers used in glazing applications arepolycarbonates (PC), polyesters like PET-G, polymethylmethacrylate(PMMA), polyvinylbutyral (PVB) and others. Mainly used for agriculturalapplications are polyolefin films.

For this purpose several NIR absorbing dyes and pigments have beenproposed and are commercially available, such as phthalocyanines andquaterrylenes (i.e.: LUMOGEN (RTM) 788 or 765 from BASF).

However these NIR-absorbers do not fully satisfy all technological andmarket requirements.

It is therefore the object of the instant invention to provide newphthalocyanines, which overcome the deficiencies of the prior artNIR-absorbers.

The present invention provides NIR absorbing phthalocyanines with strongabsorption in the NIR region whilest showing low or very low absorptionin the visible region Furthermore they combine a high compatibility witha high thermal stability and weather resistance in the most commonplastic matrices.

One aspect of the invention is a compound of formula (Ia)

R is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by one or more Oatoms, benzyl, cyclohexyl or R and R′ together with the nitrogen atom towhich they are bonded form a morpholine group;R′ is hydrogen or C₁-C₁₈alkyl;

M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu and Co

with the proviso thatif R is methyl and R′ is hydrogen, M is not Znif R and R′ are butyl or octyl M is not Sn andif R and R′ are methyl M is not Zn, Ti(O), V(O), Cu and Co.

The alkyl radicals may be linear or branched. Examples of alkylcontaining 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl,butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl,octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, hexadecyl and octadecyl.

C₃-C₁₈alkyl interrupted by O are for example derived from ethyleneglycol or propylene glycol. For example M is Mn, Cu, V(O), Co or Al.

For instance R is C₁-C₁₈alkyl; R′ is H and M is Mn, Cu, V(O), Co or Al.

In a specific embodiment of the invention R is CH₃, R′ is hydrogen and Mis Mn, V(O), Cu or Co.

The preparation of the instant phthalocyanines is carried out in analogyto known synthetic routes.

One possibility is, for example,

For some metals a second strategy is more useful:

The compounds of formula (Ia) are ideally suitable as IR-absorbers. Thegreat advantage is that these phthalocyanines lead to plastic articleswhich are highly transparent and essentially colorless.

Consequently another aspect of the invention is a transparent ortranslucent composition comprising

a) a compound of formula (I)

R is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by one or more Oatoms, benzyl, cyclohexyl or R and R′ together with the nitrogen atom towhich they are bonded form a morpholine group;R′ is hydrogen or C₁-C₁₈alkyl;

M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu and Co.

which is dispersed inb) a thermoplastic or crosslinkable polymer.

The amount of light transmitted through the present materials, i.e.degree of translucency or transparency, mainly depends on well knownparameters such as the particle loading, further additives used, hazelevel of the polymer matrix and thickness of the material. The presentmaterials usually are at least 80%, or rather more than 90% translucentin each part of the visible range (400-800 nm); preferred materials havegood transparency, and especially are selected from clear-transparentsheets and films of thickness less than 10 mm (e.g. 0.01 to 5 mm).Preferred materials further share one or more of the followingadvantageous properties:

a full solar radiation transmittance (340-1800 nm) of less than 60%,a haze of less than 1%, anda full visible light transmittance (400-800 nm) of more than 75%.

A wide variety of polymers may be used. Examples are given below.

-   -   Polycarbonate (PC) or a coating or coextruded layer on        polycarbonate, polyesters, acrylics, halogenated polymers such        as polyvinylchloride (PVC), polyolefins, aromatic homopolymers        and copolymers derived from vinyl aromatic monomers and graft        copolymers thereof such as acrylnitril-butadiene-styrene        terpolymer (ABS), containing these polymers as major component        or in essentially pure form (e.g. 50-100% b.w.), especially:    -   a polymer selected from PC, polymethylmethacrylate (PMMA),        polyethyleneterephthalate (PET, PET-G), PVC, transparent ABS,        polyvinylidene fluoride (PVDF), styrene-acrylnitril copolymer        (SAN), polypropylene (PP), polyethylene (PE) including blends,        alloys, co-polymers.

Also suitable are polyvinylacetales such as polyvinylbutyral (PVB).

Polymers useful within the present invention include the following ones:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

radical polymerisation (normally under high pressure and at elevatedtemperature).

-   -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).        2. Mixtures of the polymers mentioned under 1), for example        mixtures of polypropylene with polyisobutylene, polypropylene        with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of        different types of polyethylene (for example LDPE/HDPE).        3. Copolymers of monoolefins and diolefins with each other or        with other vinyl monomers, for example ethylene/propylene        copolymers, linear low density polyethylene (LLDPE) and mixtures        thereof with low density polyethylene (LDPE),        propylene/but-1-ene copolymers, propylene/isobutylene        copolymers, ethylene/but-1-ene copolymers, ethylene/hexene        copolymers, ethylene/methylpentene copolymers, ethylene/heptene        copolymers, ethylene/octene copolymers,        ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin        copolymers (e.g. ethylene/norbornene like COC),        ethylene/1-olefins copolymers, where the 1-olefin is generated        in-situ; propylene/butadiene copolymers, isobutylene/isoprene        copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl        acrylate copolymers, ethylene/alkyl methacrylate copolymers,        ethylene/vinyl acetate copolymers or ethylene/acrylic acid        copolymers and their salts (ionomers) as well as terpolymers of        ethylene with propylene and a diene such as hexadiene,        dicyclopentadiene or ethylidene-norbornene; and mixtures of such        copolymers with one another and with polymers mentioned in 1)        above, for example polypropylene/ethylene-propylene copolymers,        LDPE/ethylene-vinyl acetate copolymers (EVA),        LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA,        LLDPE/EAA and alternating or random polyalkylene/carbon monoxide        copolymers and mixtures thereof with other polymers, for example        polyamides.        4. Aromatic homopolymers and copolymers derived from vinyl        aromatic monomers including styrene, α-methylstyrene, all        isomers of vinyl toluene, especially p-vinyltoluene, all isomers        of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl        naphthalene, and vinyl anthracene, and mixtures thereof.        Homopolymers and copolymers may have any stereostructure        including syndiotactic, isotactic, hemi-isotactic or atactic;        where atactic polymers are preferred. Stereoblock polymers are        also included.        5. Copolymers including aforementioned vinyl aromatic monomers        and comonomers selected from ethylene, propylene, dienes,        nitriles, acids, maleic anhydrides, maleimides, vinyl acetate        and vinyl chloride or acrylic derivatives and mixtures thereof,        for example styrene/butadiene, styrene/acrylonitrile (SAN),        styrene/ethylene (interpolymers), styrene/alkyl methacrylate,        styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl        methacrylate, styrene/maleic anhydride,        styrene/acrylonitrile/methyl acrylate; mixtures of high impact        strength of styrene copolymers and another polymer, for example        a polyacrylate, a diene polymer or an ethylene/propylene/diene        terpolymer; and block copolymers of styrene such as        styrene/butadiene/styrene, styrene/isoprene/styrene,        styrene/ethylene/butylene/styrene or        styrene/ethylene/propylene/styrene.        6. Graft copolymers of vinyl aromatic monomers such as styrene        or α-methylstyrene, for example styrene on polybutadiene,        styrene on polybutadiene-styrene or polybutadiene-acrylonitrile        copolymers; styrene and acrylonitrile (or methacrylonitrile) on        polybutadiene; styrene, acrylonitrile and methyl methacrylate on        polybutadiene; styrene and maleic anhydride on polybutadiene;        styrene, acrylonitrile and maleic an hydride or maleimide on        polybutadiene; styrene and maleimide on polybutadiene; styrene        and alkyl acrylates or methacrylates on polybutadiene; styrene        and acrylonitrile on ethylene/propylene/diene terpolymers;        styrene and acrylonitrile on polyalkyl acrylates or polyalkyl        methacrylates, styrene and acrylonitrile on acrylate/butadiene        copolymers, as well as mixtures thereof with the copolymers        listed under 4), for example the copolymer mixtures known as        ABS, MBS, ASA or AES polymers.        7. Halogen-containing polymers such as polychloroprene,        chlorinated rubbers, chlorinated and brominated copolymer of        isobutylene-isoprene (halobutyl rubber), chlorinated or        sulfo-chlorinated polyethylene, copolymers of ethylene and        chlorinated ethylene, epichlorohydrin homo- and copolymers,        especially polymers of halogen-containing vinyl compounds, for        example polyvinyl chloride (PVC), polyvinylidene chloride,        polyvinyl fluoride, polyvinylidene fluoride (PVDF), as well as        copolymers thereof such as vinyl chloride/vinylidene chloride,        vinyl chloride/vinyl acetate or vinylidene chloride/vinyl        acetate copolymers.        8. Polymers derived from α,β-unsaturated acids and derivatives        thereof such as polyacrylates and polymethacrylates; polymethyl        methacrylates (PMMA), polyacrylamides and polyacrylonitriles,        impact-modified with butyl acrylate.        9. Polyesters derived from dicarboxylic acids and diols and/or        from hydroxycarboxylic acids or the corresponding lactones, for        example polyethylene terephthalate (PET), polybutylene        terephthalate (PBT), poly-1,4-dimethylolcyclohexane        terephthalate, polyalkylene naphthalate (PAN) and        polyhydroxybenzoates, as well as block copolyether esters        derived from hydroxyl-terminated polyethers; and also polyesters        modified with polycarbonates or MBS.        10. Polycarbonates and polyester carbonates, examples have been        already given above.

Suitable polyvinylacetales include polymers derived from unsaturatedalcohols and amines (i.e. acyl derivatives or acetals thereof), forexample polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine; as well as their copolymers with olefins mentioned in 1)above.

Incorporation of the compounds of formula (I) into the polymer matrixleads to plastic articles which are highly transparent; they may becolorless (e.g. for clear glazings or films) or colored, e.g. byaddition of a pigment or mixture of pigments, e.g. for applicationswherein suitable light filtering or sun screening is desired. Thepresent compounds of formula (I) allow high loading, giving access tohigh heat shielding effects.

Preferable loadings are from 0.01 to 10%, especially 0.1 to 5% by weightof the final polymer composition.

The above polymers are all thermoplastic polymers. It is however alsopossible to incorporate the instant phthalocyanines into acurable/crosslinkable coating, which is applied to a transparentsubstrate, such as glass or one of the polymers mentioned above.Examples for curable/crosslinkable coatings are given below.

1. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

2. Drying and non-drying alkyd resins.

3. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

4. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

5. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

6. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

In general thermoplastic polymers are preferred.

Preferably the thermoplastic or crosslinkable polymer comprisespolycarbonate, a coating or coextruded layer on polycarbonate,polyesters, acrylics, halogenated polymers, such as polyvinylchloride,polyolefins, aromatic homopolymers and copolymers derived from vinylaromatic monomers and graft copolymers thereof such asacrylnitril-butadiene-styrene terpolymer, and polyvinylacetales; as wellas blends, alloys and co-polymers thereof.

In a specific embodiment of the invention the thermoplastic orcrosslinkable polymer comprises polycarbonate, polymethylmethacrylate,polyethyleneterephthalate, polyvinylchloride, transparent ABS,polyvinylidene fluoride, styrene-acrylnitril copolymer, polypropylene,polyethylene, or mixtures thereof.

The composition described above may contain as further component aconventional additive selected from processing additives, antioxidants,flame retardants, clarifiers, UV absorbers and/or sterically hinderedamines. Examples are given below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl phenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl 6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylamino-methylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetra-methyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300;

where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyltetra(α-cyano-β,β-diphenylacrylate.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or with out additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetra methyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-hydrooxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor(Clariant; CAS Reg. No. 106917-31-1],5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, thereaction product of2,4-bis-[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine),1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)-amino)-s-triazine.

2.7. Oxamides, for example 4, 4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydrooxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba SpecialtyChemicals Inc.), tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate, dimistrylthiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of p-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyl-dibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxy-ethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2-acetyl-5-isooctylphenyl)-5-isooctyl-benzofuran-2-one.

Specific UV-absorbers to be mentioned in the present invention are thefollowing:

The hydroxyphenyl triazine UV-absorbers are known and are partiallyitems of commerce.

The most suitable benzotriazole UV-absorbers are commercially availableunder the Trade Names TINUVIN 213 (RTM), TINUVIN 326 (RTM), TINUVIN 900(RTM), TINUVIN 328 (RTM) and TINUVIN 350 (RTM) TINUVIN 360 (RTM),TINUVIN 571 (RTM).

One or more of these further additives are usually contained in anamount of 0.01 to about 10% of the composition, often in a concentrationlevel of about 0.1 to 5% by weight of the final composition. Importantare, for example, antioxidants (e.g. phenolic antioxidants and/orphosph(on)ites listed above) and, for many applications, flameretardants. Clarifiers/nucleating agents may be added to provide orimprove transparency, especially in polyolefin compositions. Especiallypreferred is the combination of the present phthalocyanines with lightstabilizers such as UV absorbers and/or sterically hindered amines(HALS).

In another embodiment of the invention further to the phthalocyanines offormula (I) there may be present in the composition as further componentsolid nano-scaled particles of a thickness of less than 200 nm, whichconsist of an oxide of zinc and/or a nitride of a transition metal ofgroup III, IV, V, VI of the periodic system, each of which is doped withone or more of the elements belonging to main groups III and IV of theperiodic system, or consist of undoped vanadium nitride or scandiumnitride.

In particular the nitride is selected from nitrides of scandium,yttrium, lanthanum including the lanthanides, titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum, wolfram; thedoping elements are selected from boron, aluminum, gallium, indium,thallium, carbon, silicon, germanium, tin, lead; the particle preferablyconsisting of aluminum doped zinc oxide, indium doped zinc oxide,gallium doped zinc oxide, aluminum doped titanium nitride, indium dopedtitanium nitride, gallium doped titanium nitride, aluminum dopedvanadium nitride, indium doped vanadium nitride, gallium doped vanadiumnitride, vanadium nitride, aluminum doped scandium nitride, indium dopedscandium nitride, gallium doped scandium nitride, scandium nitride.

Useful oxides are, for example, doped zinc oxides such as

AZO (Aluminum Zinc Oxide) IZO (Indium Zinc Oxide) GaZO (Gallium ZincOxide)

Examples of nitride and doped nitride materials useful as furthercomponents in the invention are the following ones:

AlTiN (titanium nitride doped with Aluminium)InTiN (titanium nitride doped with Indium)GaTiN (titanium nitride doped with Gallium)VN (vanadium nitride)AlVN (vanadium nitride doped with Aluminium)InVN (vanadium nitride doped with Indium)GaVN (vanadium nitride doped with Gallium)ScN (scandium nitride)AlScN (scandium nitride doped with Aluminium)InScN (scandium nitride doped with Indium)GaScN (scandium nitride doped with Gallium)

Normal Zinc Oxide shows no absorption in the NIR region: dopingtransforms the not conducting in a conducting material which showsabsorption in the NIR region.

Regarding the doping level, the present oxides and nitrides may berepresented by the formulae:

X_(a)Zn_(b)O_(c)  (II)

X_(a)Y_(d)N_(e)  (III)

where X is one or more of the elements belonging to main group IIIand/or IV of the periodic system, Y is a transition metal belonging togroup III, IV, V and/or VI (see above for more details of elementsbelonging to these groups); indices a-e indicate the abundance of thecomponents, with formula (II) obeying to the condition a<b<c, andformula (III) obeying to the condition a<d less or equal to e. Dopinglevels, for example of Al, Ga and/or In in ZnO or TiN, often are in therange 0.01 to about 20, especially 0.1 to 10% by weight of the finalparticle material. The nanoparticles are solid and often, but notnecessarily, cristalline. They may be prepared according to methodsknown in the art, e.g. using sputtering, thermal evaporation, chemicalvapor deposition (CVD), spray pyrolysis and sol-gel processes; thematerials often are commercially available.

Preferred materials are zinc oxide doped with Al, Ga, In; titaniumnitride doped with Al; vanadium nitride or especially scandium nitride;or vanadium nitride or especially scandium nitride doped with Al, Ga,In. Of special importance are Ga or especially Al as doping elements.

Also of special interest are the following materials: ATO (Tin oxidedoped with Antimony), ITO (Tin oxide doped with Indium), AZO (Zinc oxidedoped with Aluminum), IZO (Zinc oxide doped with Indium), GaZO (Zincoxide doped with Gallium), LaB₆ and doped tungsten oxides (YWO_(x)).Silver or gold nanoparticles, nanoprisms or nanorods, carbon nanotubes.

Such doped oxides and their use in IR shielding applications are forexample described in US 2003/0122114 and U.S. Pat. No. 7,074,351.

One or more of these materials may be used.

The nanoparticles of the oxides or nitrides used as further componentswithin the present invention are found not to interact with light asreflectors but as absorbers (scattering is present but gives only asmall contribution).

Plastic materials, especially films of the present invention, containingpolymers and nanoparticles as described above, advantageously may beused in technical application fields such as architectural glazing,glazing in building and construction, automotive glazing, transportationglazing, agricultural films and structures. The materials may be solidsheets, monolithic sheets, twin-wall sheets, multi-wall sheets, flatsheets, corrugated sheets, films, oriented or mono- or biaxiallyoriented films, lamination films, capstock films.

Specific application fields include wintergarden and veranda buildings,facades, skylights, pool covers and enclosures, roof structures, vaults,walkways, shelters, signage, interior and exterior design elements, sunshades, side window, rear window, panorama roof, greenhouses.

Main applications are heat-shielding, light management, heat management,energy management, solar control; also of importance are laser welding,security features, marking, tracers, heat transfer.

Compositions of the invention preferably are unplasticized. Compositionsof the invention do not require metals or metallic particles and usuallydo not contain such components. Of special technical interest are rigid,transparent compositions, such as plates or sheets, for automotive orarchitectural glazings, or translucent or transparent polyolefin orpolyolefin copolymer films, especially for agricultural applications.

The additives of the invention and optional further components may beadded to the polymer material individually or mixed with one another. Ifdesired, the individual components can be mixed with one another beforeincorporation into the polymer for example by dry blending, compactionor in the melt.

The incorporation of the additives of the invention and optional furthercomponents into the polymer is carried out by known methods such as dryblending in the form of a powder, or wet mixing in the form ofsolutions, dispersions or suspensions for example in an inert solvent,water or oil. The additives of the invention and optional furtheradditives may be incorporated, for example, before or after molding oralso by applying the dissolved or dispersed additive or additive mixtureto the polymer material, with or without subsequent evaporation of thesolvent or the suspension/dispersion agent. They may be added directlyinto the processing apparatus (e.g. extruders, internal mixers, etc),e.g. as a dry mixture or powder or as solution or dispersion orsuspension or melt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is preferably carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the additive or additive blend to the thermoplasticpolymer can be carried out in all customary mixing machines in which thepolymer is melted and mixed with the additives. Suitable machines areknown to those skilled in the art. They are predominantly mixers,kneaders and extruders.

The process is preferably carried out in an extruder by introducing theadditive during processing.

Particularly preferred processing machines are single-screw extruders,contrarotating and corotating twin-screw extruders, planetary-gearextruders, ring extruders or cokneaders. It is also possible to useprocessing machines provided with at least one gas removal compartmentto which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffex-trusion, Vol. 1 Grundlagen, Editors F. Hensen, WKnappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-143394 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, preferably 20-48screw diameters. The rotational speed of the screw is preferably 1-800rotations per minute (rpm), very particularly preferably 25-400 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components is added, these can be premixed or addedindividually.

The additives of the invention and optional further additives can alsobe added to the polymer in the form of a masterbatch (“concentrate”)which contains the components in a concentration of, for example, about1% to about 40% and preferably 2% to about 20% by weight incorporated ina polymer. The polymer must not be necessarily of identical structurethan the polymer where the additives are added finally. In suchoperations, the polymer can be used in the form of powder, granules,solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polymer, withor without subsequent evaporation of the solvent. A further possibilityfor incorporating the additives of the invention into polymers is to addthem before, during or directly after the polymerization of thecorresponding monomers or prior to crosslinking. In this context theadditive of the invention can be added as it is or else in encapsulatedform (for example in waxes, oils or polymers).

The materials containing the additives of the invention described hereincan be used for the production of moldings, rotomolded articles,injection molded articles, blow molded articles, films, tapes,mono-filaments, fibers, nonwovens, profiles, adhesives or putties,surface coatings and the like.

A further aspect of the invention is a process for the preparation of atransparent or translucent heat shielding material, which processcomprises the addition of a compound of formula (I) as described aboveto a thermoplastic or crosslinkable polymer.

Yet other aspects of the invention are the use of a compound asdescribed above as a heat shielding additive in a thermoplastic orcrosslinkable polymer matrix and the use of the transparent ortranslucent composition as described above as a heat shieldingarchitectural or automotive glazing or agricultural film.

In another aspect, the invention relates also to the use of compounds offormula (I) for laser welding, paper printing and security printing.

The definitions and preferences given above apply also for the otheraspects of the invention.

The following examples illustrate the invention.

A) PREPARATION EXAMPLES Intermediate Compound 1

3-nitro-aminophthalonitrile (100 g), and triethylamine (116.3 g) aredissolved in N,N-dimethylacetamide (200 ml). The mixture is stirred. Anaqueous solution of methylamine (40%) is heated and the gaseous solutionis bubbled into the reaction mixture at 30-35° C. until the startingmaterial has disappeared. The reaction is followed via thin layerchromatography (TLC), (toluene:THF 1:1). The mixture is then transferredinto 600 ml of water and let stirring for 1 h at 25° C. The precipitateis filtered and washed with water. It is then re-dispersed in xylene andheated so that the water is distilled off. Once cooled down, the productprecipitates. The crude product is filtered and washed with xylene andn-hexane, then dried under vacuum overnight at 60° C. 74 g of a yellowsolid are obtained (yield: 82%). mp: 177-179° C.

¹H NMR (CDCl₃, 300 MHz):) δ 6.77-7.56 (m, 3H); 5.0 (br s, 1H); 2.9 (d,3H).

The following intermediate compounds are prepared in analogy to theabove example.

Inter- mediate compound Structure Yield number Amine used obtained (%)m.p. (° C.) 2 NH₂Et aq

67 120-122 3 NH₂-n-Bu

93 92-94 4 NH₂-n-octyl

70 63-66 5 NH₂-Cy

34 106-108 6 Morpholine

64 168-170 7 EtO(CH₂)₃NH₂

71 67-70 8 PhCH₂NH₂

48 159-162 9 Me₂NH

84 119-121

Intermediate Compound 10;

In a 500 ml reaction flask, 130 g of the intermediate compound 1 (0.47mol) are dissolved in THF (150 ml) and methanol (50 ml) under stirring.After a few minutes, a solution 30% w/w in methanol of sodium methylate(0.28 mol) is added and ammonia is bubbled into the mixture for 8 hours.The reaction progress is followed by TLC until the complete conversionof the reactant. (Eluent: 48:16:32=toluene:methanol:THF and 4% ofammonia hydroxide concentrated).

When the reaction is completed, the solvent is removed using a rotaryevaporator. The crude product is purified by crystallization from ethylacetate and dried overnight at 50° C. under reduced pressure (yield 44%)obtaining an orange solid.

Anal. Calcd. For C₉H₁₀N₄: C, 62.05%; H, 5.79%; N, 32.16%; Found: C%=61.52%; H %=5.59%; N %=32.89%; m.p.>300° C.

Intermediate Compound 11

In a 500 ml reaction flask, 124 g of the intermediate compound 3 (0.62mol) are dissolved in THF (150 ml) and methanol (50 ml) under stirring.After a few minutes, a solution at 30% w/w in methanol of sodiummethylate (0.25 mol) is added and ammonia is bubbled into the mixturefor 12 hours. The reaction progress is followed by TLC until thecomplete conversion of the reactant (eluent:48:16:32=toluene:methanol:THF and 4% of ammonia hydroxide concentrated).When the reaction is completed, the solvent is removed using a rotaryevaporator. The crude product is purified by crystallization from ethylacetate and dried overnight at 50° C. under reduced pressure, obtaininga yellow solid.

Anal. Calcd. For C₁₂H₁₆N₄: C %=66.64%; H %=7.46%; N %=25.90%, Found: C%=65.97%; H %=7.42%; N %=26.61%; m.p.: 146-147° C.

A1) Preparation of Compound 101: 1,8(11),15(18),22(25)-TetramethylaminoManganese Phthalocyanine

3-N-methyl-aminophthalonitrile intermediate compound 1 (16 g), magnesiumchloride (3 g), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 3.8 g) arestirred together under nitrogen atmosphere for 16 h (T: 155° C.).Solvent used is n-hexanol (80 ml). After reaction time, the mixture isallowed to cool to room temperature and then filtered. Several washingcycles are performed (n-hexanol, methanol, water) with the crudematerial. The filtered product is dried under vacuum at 160° C.overnight and 16.4 g of a black powder are obtained (yield: 96%).

Anal. Calcd. For C₃₆H₂₈ClMnN₁₂: C, 60.13%; H, 3.92%; Cl, 4.93%; Mn,7.64%; N, 23.37% Found: C, 59.80%; H, 3.96%; N, 21.62%; Mn (ICP):7.73%;Cl: 4.79%.

HPLC APCI-MS (negative polarization): m/z 718; mp>300° C.; UV-VIS(DMSO): A_(max): 897 nm (ε: 82150).

A2) Preparation of Compound 102: 1,8(11),15(18),22(25)-TetramethylaminoVanadyl Phthalocyanine

3-N-methyl-aminophthalonitrile (17 g), intermediate compound 1, vanadiumchloride (4 g), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 12 g) arestirred together under nitrogen atmosphere for 16 h (T: 155° C.).Solvent used is n-hexanol (100 ml). After reaction time, the mixture isallowed to cool to room temperature and then filtered. Several washingcycles are performed (n-hexanol, methanol, water) with the crudematerial. The filtered product is dried under vacuum at 170° C.overnight and 6.0 g of a black powder are obtained (yield: 34%).

Anal. Calcd. For C₃₆H₂₈N₁₂OV: C, 62.16%; H, 4.06%; N, 24.16%; O: 2.30%;V: 7.32% Found: C, 61.79%; H, 4.32%; N, 24.25%; V (ICP): 4.75%. HPLCAPCI-MS (positive polarization): m/z (M⁺+1) 696.3. mp>300° C. UV-VIS(CHCl₃): A_(max): 824 nm (ε: 97881).

The following phthalocyanine compounds are prepared in analogy.

Compound Intermediate number number Metal UV-VIS (solv): A_(max)ε_(λmax) 103 2 Mn (CHCl₃) 876 nm 58469 104 3 Mn (CHCl₃) 881 nm 54202 1054 Mn (CHCl₃) 882 nm 60532 106 5 Mn (CHCl₃) 890 nm 68446 107 6 Mn (CHCl₃)826 nm 51171 108 7 Mn (CHCl₃) 879 nm 57255 109 1 Cu (DMSO) 782 nm 4100110 3 Cu (CHCl₃) 789 nm 44731 111 1 Al (DMSO) 822 nm 110354 112 1 Co(DMSO) 758 nm 64052 113 1 Sn (CHCl₃) 865 nm 32806 114 7 Sn (CHCl₃) 878nm 26265 115 1 Zn (CHCl₃) 772 nm 19414 116 2 Zn (CHCl₃) 775 nm 38776 1173 Zn (CHCl₃) 778 nm 91818 118 5 Zn (CHCl₃) 782 nm 110932 119 6 Zn(CHCl₃) 741 nm 68794 120 8 Zn (CHCl₃) 767 nm 73040 121 1 Ti═O (CHCl₃)834 nm 43544 122 3 Ti═O (CHCl₃) 842 nm 40691 123 4 Ti═O (CHCl₃) 814 nm76646

A3) Preparation of Compound 124: 1,8(11),15(18),22(25)-TetramethylaminoCopper Phthalocyanine

In a 250 ml reaction flask, 15 g of the intermediate compound 10 (0.086mol) are dissolved in n-hexanol (150 ml) under stirring and after a fewminutes, 3.4 g of CuCl₂ (0.02 mol) and 6.1 g of DBU (0.04 mol) areadded. The reaction is then heated, refluxed for 16 h and filtered whencooled to room temperature. The solid is washed on the filter with 50 mlof methanol for two times. The solid product is finally dried overnightat 140° C. under reduced pressure, providing 13.8 g of a black powder.

Anal. Calcd. For C₃₆H₂₈CuN₁₂: C, 62.46%; H, 4.08%; N, 24.28%; Cu, 9.18%,Found: C, 61.73%; H, 4.10%; N, 23.63%; Cu, 8.32%; HPLC APCI-MS (positivepolarization) m/z=692.1; m.p.: >300° C.; UV-Vis (DMSO): A_(max): 781 nm(ε: 3777).

A4) Preparation of Compound 125: 1,8(11),15(18),22(25)-TetrabuthylaminoCopper Phthalocyanine

In a 250 ml reaction flask, 15.0 g of the intermediate compound 11 (0.07mol) are dissolved in n-hexanol (100 ml) under stirring and after fewminutes, 3.4 g of CuCl₂ (0.02 mol) and 3.2 g of DBU (0.02 mol) areadded. The reaction is then heated at reflux for 16 h. When cooled toroom temperature 50 ml of isopropanol are added, the crude is filteredand the solid obtained is washed twice with 20 ml of isopropanol. Thesolid product is finally dried overnight at 140° C. under reducedpressure, providing 8.9 g of a black powder.

Anal. Calcd. For C₄₈H₅₂CuN₁₂: C, 66.69%; H, 6.09%; N, 19.53%; Cu 7.38%;Found: C, 63.84%; H, 6.01%; N, 20.07%; Cu, 6.88%. HPLC APCI-MS (positivepolarization) m/z=860; m.p.: 250° C. (R) 280°-290° C.; UV-Vis (CHCl₃):A_(max): 789 nm (ε: 44731).

B) APPLICATION EXAMPLES B1) Examples of PC Injection Molding/PC FilmExtrusion Mixing and Compounding

3.0 kg of milled polycarbonate (Makrolon 3103) are dried in a vacuumoven at 120° C. for 8 hours. The powder is mixed with the additiveslisted in Table B1 for 3 minutes at 80° C. in a 51 Henschel Turbomixerand afterwards compounded on a Berstorff ZE 25×32D at 280° C. Thepolymer strand is granulated.

Sheet Extrusion

The pellets are used to produce a 100 μm thick cast film (platte) on aCollin CR-136/350 sheet extrusion line at a maximum temperature of 280°C.

Artificial Weathering

The samples are irradiated in a Weather-Ometer Ci65 from ATLAS inaccordance with ASTM G 155/ASTM G 151, Xenon lamp with 2 borosilicatefilters, 0.35 W/m2 at 340 nm, 63±3° C. black panel temperature, 102 mindry and light, 18 min water spray and light.

Evaluation

The ΔE values are measured in accordance with DIN 6174.

The UV-VIS-NIR Spectrum is recorded on a Shimadzu UV 3101 UV withISR3100 integrating sphere: Parameter: Slit width 20, wavelength250-1800 nm, Scan speed fast, Light Source change at 360 nm and Detectorchange at 830 nm.

The relative absorption is calculated by the absorption at the maximumdivided by the initial absorption at the same wavelength.

Haze is measured on a Haze-gard plus from Byk Gardner in accordance withASTM D-1003. the results are presented in Table B2.

PC Film sample, Thickness 100 μm: Initial values

TABLE B1 Initial Absorption Max. TINUVIN Structure Conc. [%] Haze [%] atmax. [nm] 360 [%] 101 0.03 1.3 0.158 867 5 101 0.05 1.9 0.241 867 5 1010.1 4.6 0.358 867 5 102 0.1 0.6 0.862 828 5 103 0.05 0.4 0.350 870 5 1030.1 2.0 0.703 870 5 104 0.1 0.6 0.689 878 5 105 0.1 0 0.534 873 5 1070.05 0.4 0.200 830 5 107 0.1 0.5 0.404 830 5 108 0.1 2.2 0.527 871 5PC Film sample, Thickness 100 μm: aged samples

TABLE B2 Haze after ΔE after Rel. Absorption after Conc. 500 hours 500hours 500 hours Structure [%] WOM wet WOM wet WOM wet 101 0.03 0 0.3 94%101 0.05 2 0.6 96% 101 0.1 4.5 0.7 90% 102 0.1 1.5 1.6 93% 103 0.05 1.11.7 83% 103 0.1 1.7 2.2 99% 104 0.1 0.2 3.1 93% 105 0.1 0.5 3.5 92% 1070.05 1.0 4.1 77% 107 0.1 1.0 6.0 73% 108 0.1 0.3 3.0 86%

B2) Examples of MMA Polymerization Sheet Preparation

70 g freshly distilled methylmethacrylate is polymerized with 0.1%lauroylperoxide, 0.15% TINUVIN P, 0.15% TINUVIN 770 and 0.01% Compound102. after degassing. Firstly the mixture is prepolymerized at 60° C. ina twist-off glass for ca. 2 hours and then in a second step the syrup ispolymerized between glass plates at 60° C. in a water bath followed 15hours in oven followed by the final polymerization: 3 hours oven 120°C., resulting in a final thickness of ca. 1.8 mm.

Artificial Weathering

The samples were then irradiated in a Weather-Ometer Ci65 from ATLAS inaccordance to ASTM G 155/ASTM G 151, Xenon lamp with 2 borosilicatefilter, 0.35 W/m2 at 340 nm, 63±3° C. black panel temperature, dry cyclewith relative humidity of ca. 50-60%)

Evaluation

The ΔE value was measured in accordance to DIN 6174

The UV-VIS-NIR Spectrum was recorded on a Shimadzu UV 3101 UV withISR3100 integrating sphere: Parameter: Slit width 20, wavelength250-1800 nm, Scan speed fast, Light Source change at 360 nm and Detectorchange at 830 nm.

TABLE B3 ΔE after Rel. Absorption Conc. Absorption Max. TINUVIN 360 [%]500 hours % after 500 hrs Structure [%] at max. [nm] TINUVIN 770 [%] WOMwet WOM wet 102 0.01 0.141 800 0.15/0.15 6.3 89

B3) Examples of Pet-G Film Extrusion

PET-G powder (Eastar 6763 from Eastman), 1% Tinuvin 1577, 0.1% of1,8(11),15(18),22(25)-Tetramethylamino manganese phthalocyanine(compound 101) are turbo-mixed, dried at 70° C. for 12 hours, thencompounded in a twin screw Collin Extruder.

The obtained pellets are dried again and extruded in a Collin cast lineto get a 300 micron PET-G film.

C) EVALUATION OF HEAT SHEALDING

Samples containing solar controlling additives were evaluated using aninternal equipment (see FIG. 1). This instrument compares thetemperature build up of a black aluminum panel behind two plasticsamples (A4 size), one sample containing the solar controlling additivethe other being a reference without any additive. The two samples aremounted on the front side of two different chambers that are exposed tolight of a 500 W halogen lamp with color temperature of 5000 K. To havethe best accuracy two probes PT100 connected to a PC data logger areused.

1. A compound of formula (Ia)

wherein R is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by one ormore O atoms, benzyl or cyclohexyl; R′ is hydrogen or C₁-C₁₈alkyl; or Rand R′ together with the nitrogen atom to which they are bonded form amorpholine group; and M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu or Co;with the provisos that if R is methyl and R′ is hydrogen, M is not Zn,if R and R′ are butyl or octyl M is not Sn and if R and R′ are methyl Mis not Zn, Ti(O), V(O), Cu or Co.
 2. A compound according to claim 1wherein M is Mn, Cu, V(O), Co or Al.
 3. A compound according to claim 1wherein R is C₁-C₁₈alkyl; R′ is H and M is Mn, Cu, V(O), Co or Al.
 4. Acompound according to claim 1 wherein R is CH₃ R′ is hydrogen and M isMn, V(O), Cu or Co.
 5. A transparent or translucent compositioncomprising a) a compound of formula (I)

wherein R is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by one ormore O atoms, benzyl or cyclohexyl; R′ is hydrogen or C₁-C₁₈alkyl; R andR′ together with the nitrogen atom to which they are bonded form amorpholine group; and M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu or Co;which is dispersed in b) a thermoplastic or crosslinkable polymer.
 6. Acomposition according to claim 5 wherein the thermoplastic orcrosslinkable polymer comprises polycarbonate, a coating or coextrudedlayer on polycarbonate polyesters acrylics halogenated polymers,polyolefins, aromatic homopolymers, copolymers derived from vinylaromatic monomers, polyvinylacetales or blends, alloys or co-polymersthereof.
 7. A composition according to claim 5, wherein thethermoplastic or crosslinkable polymer comprises polycarbonate,polymethylmethacrylate, polyethyleneterephthalate, polyvinylchloride,transparent ABS, polyvinylidene fluoride, styrene-acrylnitril copolymer,polypropylene, polyethylene or mixtures thereof.
 8. A compositionaccording to claim 5 wherein the compound of formula (I) is present inan amount from 0.01 to 10% by weight, based on the weight of thethermoplastic or crosslinkable polymer.
 9. A composition according toclaim 5, containing as further component a conventional additiveselected from antioxidants, flame retardants, clarifiers, UV absorbersand/sterically hindered amines.
 10. A composition according to claim 5containing as further component solid nano-scaled particles of athickness of less than 200 nm, which consist of an oxide of zinc and/ora nitride of a transition metal of group III, IV, V or VI of theperiodic system, each of which is doped with one or more of the elementsbelonging to main groups III or IV of the periodic system, or consist ofundoped vanadium nitride or scandium nitride.
 11. A compositionaccording to claim 10 comprising a nitride which is selected fromnitrides of scandium, yttrium, lanthanum, lanthanides, titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand wolfram; and where the doping elements are selected from boron,aluminum gallium, indium thallium, carbon, silicon, germanium, tin andlead.
 12. A composition according to claim 5 containing as furthercomponent tin oxide doped with antimony (ATO), tin oxide doped withindium (ITO), zinc oxide doped with aluminum (AZO), zinc oxide dopedwith indium (IZO), zinc oxide doped with gallium (GaZO), LaB₆, dopedtungsten oxides (YWO_(x)), silver or gold nanoparticles, nanoprisms ornanorods or carbon nanotubes.
 13. Architectural or automotive glazing inform of a solid plate or sheet, a monolithic sheet, a twin-wall sheet, amulti-wall sheet, a flat sheet or a corrugated sheet; or an agriculturalfilm in form of a mono- or biaxially oriented film, a laminated film ora capstock film, comprising a composition according to claim
 5. 14.Process for the preparation of a transparent or translucent heatshielding material, which process comprises the addition of a compoundof formula (I)

wherein R is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by one ormore O atoms, benzyl or cyclohexyl; R′ is hydrogen or C₁-C₁₈alkyl; or Rand R′ together with the nitrogen atom to which they are bonded form amorpholine group; and R′ is hydrogen or C₁-C₁₈alkyl and M is Mn, Zn,V(O), Ti(O), Si, Al, Sn, Cu or Co; to a thermoplastic or crosslinkablepolymer. 15-17. (canceled)
 18. A composition according to claim 10wherein the particles consist of aluminum doped zinc oxide, indium dopedzinc oxide, gallium doped zinc oxide, aluminum doped titanium nitride,indium doped titanium nitride, gallium doped titanium nitride, aluminumdoped vanadium nitride, indium doped vanadium nitride, gallium dopedvanadium nitride, vanadium nitride, aluminum doped scandium nitride,indium doped scandium nitride, gallium doped scandium nitride orscandium nitride.